Sensitized photographic emulsion containing color couplers



Patented June 2, 1953 SENSITI-ZED;BHQEBOGRAPHIC EMULSION CONTAINING.GOLOR COUPLERS J'olin Spence' and- Burt H. Carroll, Rochester, N; Y.',assignots= to- Eastman Kodak Company, Rochester; N. 13., acorporationofi New. Jersey No,.Drawing, Application August 29, 1947,Serial/BNO. 771,380

This inventionrelates to spectrally- (optically) sensitized photographicsilverhalide: emulsions containing'color couplers.

In general, in subtractive color photography" blue; green and redsensitive photographic silver halide: emulsions-are employed; The greenand red-sensitivities are obtained bythe use offs-ensi: tizing dyesadsorbed; to the silver halidegrain-s. When couplers or dispersions ofcouplers" are incorporated'inthe dye-sensitizedemulsions; it isnecessary that; they do not alter the spectral; (optical) sensitizationproduced by the dyes;

With the: very great: majority of sensitizing dyes; themolten sensitizedsilver halide emulsions in combination with the color couplers ordispersions of color couplers are not stable enough" to permit? theobtaining of" uniform sensitivitythroughout the" period of coating;.the*emulsions losing; the sensitivity conferred" by the dye-to aconsiderable degree during'the coating: operation;

We have now "found that certain combinations: of silver halide emulsionssensitizing dyes and color couplers are, in fact, stable and". thatithemelted-emulsions can be coatedwithoutappre ciable loss indye-sensitivity;

It is, accordingly, an object of our 'inventiontoprovide stablecombinations of silver halide emulsions sensitizing dyes and-colorcouplers: A further object is to provide a process for preparing such:combinations. Still other. objects will become apparent hereinafter.

' In: accordance with our invention a weprepare an emulsion for colorphotography comprising a red-sensitive silverhalide emulsion containinga; color-former (coupler) for thecyan-image (i.- e'; arcoIon-iormer.capable offorming a quinoneiinine dye with a phenylenediaminedeveloper), said redesensitivo emulsion being sensitized with atleastone sensitizing dye selected from the group consisting of those. dyes:represented by the fol- 3 lowing general formulas:

and R4 each represents a member selected from theegroup; consisting;ofhydrogen atom and. an: alkyli group. containing; from 1 tor-4. carbon;atoms,x g-:-.methy ethyl, neprcpyl, isobutyl and.nsbutylu Z and? Z1eachrepresents non-metallic. atoms-- necessary to complete a.heterocyclic nucleus; selected: from the group, consisting of: hetero.cyclidanucleiofthe benzothiazole series; hetero.- cyclic; nuclei-of;thebenzoselenazme series, hetero:-- cyclic; nuclei; of.thenaphthothiazole; series anda heterocyclic nuclei-1 of thenaphthoselenazole; series. e; g. the benzothiazole nucleus, the:v5;methylbenzothiazole= nucleus, the 5methoXy, benzothiazole nucleus, the5-ethy1benzothiazole, nucleus,-, the: 5-ethoxybenzo.thiazo1enucleus;.the 5 .-phenylbenzothiazolenucleus, the. 5-chloro.- benzothiazolenucleus; the-5r-bromobenzothiazole nucleus, the benzoselenazole nucleus,the 5. OhlOIObGI'lZOSBIEIIflZOlB? nucleus; the. aenaphthothiazole,nucleus, the; fl-naphthothiazole nucleus,, the a-naphthoselenazo1e--nucleus,,' the ;3-naph.-:--- thoselenazole nucleus, etc;, R1 andvRa eachreprersents: an alkyl group; containing from: 1' to, 2, carloon. atomsmie, methylandethyl, R2--.I'61D1'6.-- sents; a: monocyclic aryl; group" ofthe benzene. series; e: g;.nheny;l-,- p-methoX yphenyl, mi-tolyl,pechloropheny-h, prethoxyphenyl, p-tolyh. pebromophenyl, and; X,represents ananion, e,-. g, chloride, bromide, iodide,. methylsulfata.ethyl-- sulfate; p-toluenesulfonatm. benzenesulfonate acetate-,-propionate,-, thiooyanate; perchlorate, etc;

In accordancewith; our invention, we. prepare: a. yellow-greensensitiveTsilver halide. emulsion; containing a:, color-former (coupler) for. the:magenta. image? (ii er. a color-former capable, of= forming: an;azomethine dye" with. a, phenylenea diamine; developer), saidyellow-green sensitive,

silver halide emulsion being sensitized with at;-

least'.onesensitizingdyeselected from the group consistinggof;thosezdyes'represented by the fol-.

lowing, general formulas:

wherein R4 and R each represents an alkyl group containing from 1 to 4carbon atoms, e. g. methyl, ethyl, n-propyl, n-butyl, isobutyl, etc., X1represents an anion, e. g. benzenesulfonate, p-toluenesulfonate,chloride, bromide, iodide, perchlorate, methylsulfate, ethylsulfate,thiocyanate, acetate, propionate, etc, D2 and D3 each represents adivalent hydrocarbon radical containing from 1 to 4 carbon atoms, e. g.methylene, ethylene, ethylidene, trimethylene, tetramethylene, etc., andZ3 represents the non-metallic atoms necessary to complete aheterocyclic nucleus of the quinoline series, e. g. the quinolinenucleus, the fi-methylquinoline nucleus, the G-ethylquinoline nucleus,the G-methoxyquinoline nucleus, the 6- ethoxyquinoline nucleus, theG-chloroquinoline nucleus, etc.

In the preparation of photographic elements for color photographyemploying our new emulsions, any of the customary procedures can beused. Thus, the emulsions can be coated on a support as separate layers,e. g. a support (of cellulose acetate film, resin film, paper, etc.) canbe coated with a layer of the red-sensitive emulsion containing a colorformer (as described above) and upon this, a layer of the yellow-greensensitive emulsion containing a color former (as described above) can becoated. Upon the yellowgreen sensitive layer, a yellow filter layer canthen be coated and upon the filter layer a layer of a blue sensitiveemulsion containing a colorformer which produces a yellow image orpicture. Typical multi-emulsion photographic elements (involvingcolor-formers in the emulsion) to which our invention is applicable aredescribed in United States Patents 1,055,155, dated March 4, 1913;2,304,940, dated December 15, 1942, and 2,322,027, dated June 15, 1943.

Our invention is also applicable to color photographic emulsion materialwherein the emulsions are mixed instead of disposed in separate layers.Moreover, our invention is also applicable for producing singleemulsions containing colorformers for making component color pictures.In addition to the sensitizing dyes and color-formers the emulsionsemployed in our invention can also contain the usual additions toemulsions, e. g. stabilizers, etc.

Our invention is especially useful where the emulsions contain, inaddition to a color-former, a dispersing agent for the color-former, e.g. the water-insoluble but water-permeable materials set forth in U. S.Patents 2,304,940 and 2,322,027, such as water-insoluble butwater-permeable cellulose esters, e. g. water-insoluble, butwaterpermeable cellulose acetate, cellulose acetatephthalate, cellulosenitrate, etc., water-insoluble, but water-permeable cellulose ethers,water-insoluble but water-permeable natural and synthetic resins,high-boiling, substantially waterinsoluble crystalloidal materials, suchas N-namylphthalimide, tetrahydrofurfuryl benzoate, triphenyl phosphate,n-butyl sulfone, ethyl-N,N- di-n-butylcarbamate,ethyl-N-phenylcarbamate, tetrahydrofurfuryl succinate, ethyl benzylmalonate, methyl phthalate, n-butyl phthalate, namyl phthalate,p-methoxyethyl phthalate, pethoxyethyl phthalate, fi-butoxyethylphthalate, butyl o-methoxybenzoate, n-hexyl benzoate, benzophenone, psec amylbenzophenone, tricresyl phosphate, diphenyl mono-p-tert. butylphenyl phosphate, monophenyl di-o-chlorophenyl phosphate,tri-o-phenylphenyl phosphate, ptoluenesulfonyl methyl-o-toluidine,p-toluenesulfonyl dimethylamide, p,p'-di-n-amylbenzenesulfonamide,p-toluenesulfonyl di-n-butyl amide, N,N'-diethyl-N,N'-diphenyl urea,N,N-di-n-butyl urea, etc.

Our invention is especially useful with emulsions in which thecolor-former is dispersed in one or more of the aforesaid substantiallywaterinsoluble, high-boiling crystalloidal materials. Thesecrystalloidal materials are organic and have boiling points above about175 C. These crystalloidal materials have a high solvent action for thecolor-formers and for the dyes formed therefrom and are permeable tophotographic processing solutions. These crystallcidal materials havebeen referred to as oil formers because they have the property ofproducing an oily or liquid solution when mixed with the coupler, eventhough the coupler is a solid. The crystalloidal materials are generallyliquid at ordinary temperatures or low melting solids (below 0.). Themost useful compounds contain one or more polar groups such as halogen,hydroxyl, carboxylic acid, amide, ketone, etc.

The following couplers are suitable for use in our invention. It is tobe understood that this list is not exhaustive, but merely to typifycompounds which may be used.

Couplers producing cyan images 5- 11:-amylphenoxybenzenesulfonamino)-1-naph- 5-(N benzyl N naphthalenesulfonamino)-1- naphthol 5-(n-benzyl-N-n-valerylamino) l-naphthol 5-caproylamino-1-naphthol2-chloro-5-(N-n-valeryl N pisopropylbenzylamino) -1-naphthol 2,4dichloro-5- (p-nitrobenzoylB-o-hydroxyeth- .vlamino) -1-naphthol2,4-dichl0ro-5-palmithylaminol-naphthol2,2'-dihydroXy-5,5'-dibromostilbene5-diphenylethersulfonamido-1-naphthol l-hydroxy-Z- (N-isoamyl-N-phenyl)naphthamide l-hgdroxy-2- (N-p-sec. amylphenyl) -naphtham- 8hydroxy-l-a-naphthoyl 1,2,3,4 tetrahydroquinoline2-lauryl-4-chlorophenol 1-naphthol-2-carboxylic-a-naphthalide1-naphthol-5-sulfo-cyclohexylamide 5-phenoxyacetamino-l-naphthol5-,6-phenylpropionylamino-1-naphtholMonochlor-5-(N-'yphenylpropylN-p-sec.-amylbenzoylamino) -1-naphtholZ-acetylamino-5-methylphenol 2-benzoylamino-3,5-dimethylphenol 2 s(ptert. amylphenoxy') -'n butyrylamino-5- methylphenol any of thecolor-formers producing yellow-images can be used, e. g.

Couplers producing yellow images The aforesaid couplers give colordevelopment with color developers, such asN,N-dimethyl-pphenylenediamine, N,N-diethyl p phenylenediamine,N-carbamidomethyl-N-methyl-p-phenylenediamine, N-carbamidomethyl-W-tetrahydrofurfuryl-2-methy1-p-phenylenediamine, Nethyl-N -carboxymethyl2-methyl-p-phenylenediamine, N -carbamidomethyl-4-ethy1-2-methyl- 8 EXAMPLE 1 VIII.

OOH

VIII-A.

CH; IX-A.

TABLE A [Exposure through red filter which transmits substantially nolight of wavelength shorter than 530 m,u.]

Dye

VIII vI II-A IX IX-A Speed Speed 7 Speed Speed tized with same dye andcontaining a dispersion of an o-acylaminophenol coupler for cyan image,held 2 hrs. at C 2 Red speed too low to measure.

p-phenylenediamine, N -ethyl-N -tetrahydrofurto Fr m t e d in the a etable it s app t fury1-2-methyl-p-aminophenol, 3-acetylamino-4-aminodimethylaniline,N-ethyl-N-fi-methanesulfonamidoethyll-aminoaniline,N-ethyl-N-flmethanesulfonamidoethy1-3-methyl 4 aminoaniline, the sodiumsalt of N-methyl-N-fi-sulfoethyl-p-phenylenediamine, etc.

The following examples demonstrate the that two otherwise excellent redsensitizers (dyes VIII and IX) do not give emulsions which aresufficiently stable to be coated in the presence of color formers,whereas dyes VIII-A and IX-A give emulsions of satisfactory stability.

EXAMPLE 2 stability of emulsions containing color formers s prepared inaccordance with our invention. The

dyes hereinafter formulated will be referred to C1 C CH=CH CH=C in thesubsequent examples by the Roman numerals assigned to the dyes. Incertain of the exl amples comparisons with other sensitizing dyes E showthe greatly superior stability of our new CH; emulsions.

1.1 The data in the above Table show two yellowgreen sensitizers eitherof which gives an emulsion containing a coupler for the magenta image,

which emulsions are satisfactory for coating purposes.

EXAMPLE 4 XIV.

TABLE D [Exposure through red filter which transmits substantially nolight of wavelength shorter than 580 m n] Dye Speed 7gelatino-silver-bromoiodide emulsion sensitized with dye XIVgelatino-silver-broxniodide emulsion sensitized with dye XIV andcontaining a dispersion of an o-acylaminophenol coupler for cyan image,held at 1 hr. for 40 C gclatindsilvenbromiodide emulsion sensitized wlthdye XIV and containing a dispersion of an o-acylaminophenol coupler forcyan lmage, held at 2 hrs. for 40 C 1 Concentration of sensitizing dyeis mg. per liter of emulsion in all cases. In the above Table D it isshown that dye XIV gives a stable emulsion in the presence of colorcouplers for the cyan image.

EXAMPLE 5 E osure throu h red filter which transmits substantially nolight xp 51 wavelength shorter than 580 11311.]

Dye Speed 7 gelatino-silver-bromoiodide emulsion sensltized with dye XV1 same gelati o-silver-bromolodlde emulsion sensitized with same dye andcontaining a dispersion of an oacylaminophenol color coupler for cyanimage, held at C. for l hr same gelatino'silver-bromolodlde emulsionsensitized with same dye and containing a dispersion of ano-acylaminophenol color coupler for cyan image, held at 40 C. for 2 hrs.0.55

v 1 Concentration of dye in all cases, 30 mg. per liter of emulsion. Inthe above Table E it is shown that dye XV hol and a volume of the methylalcoholic solution (which may be diluted with water) containing from 5to 100 mg. of the dye or dyes is slowly added to 1000 cc. of emulsionwith stir-ring. In the case of the dyes of Formulas I, V, VI and VII, awater-soluble salt of the dyes is advantageously formed and dissolved inWater, methyl alcohol or ethyl alcohol. The resulting solution of thewater-soluble salt is then dispersed in the emulsions, The water-solublesalts are advantageously formed by adding to the dye or dyes (Wet with alittle water, methyl alcohol or ethyl alcohol), an alkali metalhydroxide, e. g. sodium or potassium hydroxide, or ammonium hydroxide,or an amine, e. g. methylamine, ethylamine, dimethylamine, diethylamine,trimethylamine, triethylamine, ethanolamine, diethanolamine,triethanolamine, pyridine, N-methylpiperidine, npropylamine,isopropylamine, n-butylamine, ethoxyethylamine, etc. The salt whichforms is then taken up in a suitable solvent, e. g. water, methylalcohol, ethyl alcohol, a mixture of methyl alcohol and water, a mixtureof ethyl alcohol and water, etc. As in the case of the dyes of FormulasII, III and IV, the dyes of Formulas I, V, VI and VII are ordinarilyemployed in a concentration of from 5 to 100 mg. per liter of emulsion.In the case of any of the sensitizing dyes employed in our invention,the optimum sensitizing effect is ordinarily obtained at a concentrationof from 5 to mg. of dye per liter of emulsion.

The sensitizing dyes in most cases should be added to the emulsionsbefore the coupler of coupler dispersion is added.

The color-formers (couplers) are incorporated in the emulsions in thecustomary manner, e. g. by adding a dispersion of the coupler in awaterinsoluble but Water-permeable material (see above) to the emulsion,or by adding a dispersion of the alkali metal of the coupler in water.When employing dispersions of couplers in the aforesaid crystalloidalmaterials, the coupler (color former) which has been mixed with thehighboiling organic crystalloidal material to produce an oil-likemixture can be dispersed in water or gelatin solution or in any aqueousbinder of col-' loidal character which is miscible with the silverhalide emulsion. The dispersion can be effected with the aid of ahomogenizer, colloid mill or the like, and the dispersions can bestabilized by the addition of emulsifying agents such as those of thewell-known higher fatty alcohol sulfate type. The dispersion may also beformed by dispersing a solution of coupler and crystalloidal material ina solvent of low boiling point such as butyl acetate with Water orgelatin solution and subsegives a fairly stable emulsion in the presenceof color couplers for the cyan image.

In preparing emulsions in accordance with our invention, the sensitizingdyes can be added to the emulsions in accordance with customary pro.-cedures, i. e. by adding a solution of' the dye inan apropriate solventto the emulsions. In the case of the dyes of Formulas II, III and IV,the

dyes are advantageously dissolved in methyl alcoquently removing thelow-boiling solvent by evaporation. I-lere also an emulsifying agent canbe used. It is important that the mixture of coupler and crystalloidalmaterial be a liquid at ordinary r temperatures, so that liquidparticles are formed when the mixture of coupler and crystalloidalmaterial is emulsified in water and mixed with the emulsion, theparticles retaining the couplerin solution, yet being readily penetratedby the photographic developing solution and other processing baths. Thenature and proportions of the coupler and the crystalloidal materialshould be chosen so that the particles are liquid under the conditionsof coating and processing the emulsion.; With the aforesaidcrystalloidal materials, there is little or no tendency tocrystallization even when the coupler is present in a proportionamounting to 50% or more of the high-boiling crystalloidal material. Thecrystalloidal ma- *terials'shou1d also hesubstantially"colorlessandstable *toward light, "heatand moisture, in addition to-b eing" in'erttothevarious'processingbaths which may be "encountered, ."suh asdevelopers,

"ozddizeddevelopers;silverremoval baths'and fixohlorobromide,tzhlorobromiodide, '-"iddochloride,-

brorriide and bromiodide "developing-out :emul- 'sions. These"ordinarily employed "silver halide developing out "emulsions "are'--emi'1lsions "which "form surface latent image- (see '-'-British1atent581L772, accepted OtOb-er "24, 194-6) iI-Iowever, l

silver "halide emulsions which 1 form latent image mostly inside thesilver 'hali'de'grains see'British Patent 581,772 supra) "can also "beemployed in praetiing our invention.

-The dyes set forth urider-Formula-II above are deseribed in thecopending 'applieationo-fheslie S. "Brooker and Frank L. -White, Serial"No. 5191354, filed J anuary 22, 19'44, now '11. SR-Patent 25478;.3'66,issued Aug-inst ll, 1949. The "dyes-set forth 1 under Formulalll aboveare described in Unitedstates Patent 252 ISEZSBfiiateWSeptember -3,"1940. "The dyes set forthunder Formulal above "can be prepared as"describedin United States Patent"'2;2'3 lififisydated 'flebruary 11,1941, by condensing a -.cyclammonium arearboxyalkyl quaternary saltcontaining a reactive methyl group :with ethyl -orthc'iformate, tethylorthoacetate;'ethyl'orthopropionate, ethylconthobdtyrate or ethylorthovalerate. The dyes set forth under Formulas IV-VIII above areprepared as described in the copending application of Gertrude VanZandtrand Leslie G. S. Brooker, Serial No. 711,816, filed November 22,1946, now U. S. Patent 21'51559153, issued 31115 1 811950.

Vlrhat"weclairrras our mvention am'didesirefito beisecured byLettersPatenttdf'tthe UnitedTStates is:

1. "A red sensitive gelatino=silver halide femulsion for"color'photography-containing dispersed therein finely divided liquid partiolesof "a".mixture of "a phenolic "icolorifornrer for "the 'fcyan image"capable :of forming 1a, rquinoneimine tr lye with i a'jphenylene'diamine developer, raifd'ra rsnb- 'stantiallywater-insoluble,- Iow"molecular weight, organic, crystalloidal' material"having .a'bo'iling point "above'about t175"C.,"saidcrystalloidahmatei-ial having a "hiE'hSOIVEHT;i2IOti0n"fOr' 'thecolorformer and for the "dye formed therfrom, :and being;permeable'tophotographic processing-solutions, "the nature andproportions'i'o'f the colorformerand"crystalloidalmaterialtbeingso.chosen that particles thereofare liquid'underrconditi'ons of coatingandprooessin'gthe "emuison safdred sensitive emulsion being sensitizedato the red with at least onesensitizing dye selected from the group consisting of those dyesrepresented by the following general formulas:

ienwon gphatim-hydro carhonzradicalac'ontainingrom $1 '"to z-ldtcarbonatoms, R :and :R4 :represent a member selected; fromathe; group:consistingto'fa; hydrogen atom and; anzvalkyl-groupccontaining .from l-130 cazrbomatomsrZtsandzzr'mchirepresents the non- :metallio. atoms."necessary "to complete a, hetero-EGYOHCZIIHOIGHSrfSElEGti-Bd.fflf'fimltheJg'I'Ou'pCOIlSiStiflgpiifiheterocyclicrnnlei ofrthesbenzothiazole series,lheterooyclicsnucleizoftthellaenzoselenazole-lseries; heterocyolicmuolei30f the inaphthothiazoletser'ies andxheterocyelic miclei'of'lthenaph'thoselenazole .series Rl and Rszeaohmepresents: anual'kylggroupcontaining'zfrom 1 to 2Jcarbonsatoms,iRzrrepre- 'sents 15a :monooyclic:;aryl groupof the benzene series, and.Xxrepresentsamanion.

A yellowegreenxsensitivevgelatino silver T-halide tiemulsion for :coloraphotography 2 containing dispersed :ztherein 'sf'fine'ly divided 1liquid ip'artieles .of satmixturerof-ia ketomethylene color-formeriiorthe magentaimage capableof forming:aiquinoneimine idye :with aphenylenediamine developer, and a substantially watersinsoluble, lowmolecular :weight, organic, zcrystalloidalrmaterialrhaving a, boilingpoint .cabove 53130-1113 1 C1, zisaid tony-stalloidal material having ahigh :solvent action for the color former and for the dye formedtherefrom, and being ermeable'to photographic processing solutions, thenature and proportions of the colonformewandicrystalloidatmaterial beingso chosen that particles thereof are liquid under conditions oflcoatingand processing the emulsion, said yellow-green sensitive emulsion beingsensitizdto the yellow-greemwith at leastonessensitizingdyesselectedzfrometlaezgrou :conv sisting of those dyesrepresented by .the followinglgeneral formula:

iv-m-ooon wherein R4 and R each represents an alkyl group containingfrom 1 to 4 carbon atoms, X1 represents an anion, D2 and D3 eachrepresents a divalent aliphatic hydrocarbon radical containing from 1 to4 carbon atoms, and Z: represents the non-metallic atoms necessary tocomplete a beterocyclic nucleus of the quinoline series.

3. A red sensitive gelatino-silver-halide emulsion for color photographycontaining dispersed therein finely divided liquid particles of amixture of an o-acylaminophenol color-former for the cyan image capableof forming a quinoneimine dye with a phenylenediamine developer, and asubstantially water-insoluble, low molecular weight, organiccrystalloidal material having a boiling point above about 175 C., saidcrystalloidal material having a high solvent action for the color-formerand for the dye formed therefrom, and being ermeable to photographicprocessing solutions, the nature and proportions of the color-former andcrystalloidal material being so chosen that particles thereof are liquidunder conditions of coating and processing the emulsion, said redsensitive emulsion being sensitized to the red with at least onesensitizing dye represented by the following general formulas:

wherein D and D1 each represents a divalent aliphatic hydrocarbonradical containing from 1 to 4 carbon atoms, R and R4 represent a memberselected from the group consisting of a hydrogen atom and an alkyl groupcontaining from 1 to 4 carbon atoms, Z and Z1 each represents thenon-metallic atoms necessary to complete a beterocyclic nucleus selectedfrom the group consisting of heterocyclic nuclei of the benzothiazoleseries, heterocyclic nuclei of the benzoselenazole series, heterocyclicnuclei of the naphthothiazole series and heterocyclic nuclei of thenaphthoselenazole series, R1 and R3 each represents an alkyl groupcontaining from 1 to 2 carbon atoms, R2 represents a monocyclic arylgroup of the benzene series, and X represents an anion.

4. A red sensitive gelatino-silver-halide emulsion for color photographycontaining dispersed therein finely divided liquid particles of amixture of an o-acylaminophenol color-former for the cyan image capableof forming a quinoneimine dye with a phenylenediamine developer, and asubstantially water-insoluble, low molecular weight, organiccrystalloidal material having a boiling point above about 175 0., saidcrystalloidal material having a high solvent action for the color-formerand for the dye formed therefrom, and being permeable to photographicprocessing solutions, the nature and proportions of the color-former andcrystalloidal material being so chosen that particles thereof are liquidunder conditions of coating and processing the emulsion, said redsensitive emulsion being sensitized to the red with at least onesensitizing dye selected from the group consisting of those dyesrepresented by the following general formula:

ooCn-1:oon=d-on= iI-nooon wherein D represents a'saturated divalentaliphatic hydrocarbon radical containing from 1 to 4 carbon atoms, Rrepresents a member selected from the group consisting of a hydrogenatom and a primary allrvl group containing from 1 to 4 carbon atoms, andZ represents the non-metallic atoms necessary to complete a heterocyclicnucleus of the benzothiazole series.

5. A red sensitive gelatino-silver-halide emulsion for color photographycontaining dispersed therein finely divided liquid. particles of a mix-;ture of an 'o-acylaminophenol color-former for the cyan image capable offorming a quinoneimine dye with a phenylenediamine developer, and asubstantially water-insoluble, low molecular weight, organiccrystalloidal material having a boiling point above about C., saidcrystalloidal material having a high solvent action for the color-formerand for the dye formed therefrom and being permeable to photographicprocessing solutions, the nature and proportions of the the color-formerand crystalloidal material being so chosen that particles thereof areliquid under conditions of coating and processing the emulsion, said redsensitive emulsion being sensitized to the red with at least onesensitizing dye selected from the group consisting of those dyesrepresented by the following formula:

' c00- OOH 6. A red sensitive gelatino-silver-halide emulsion for colorphotography containing dispersed therein finely divided liquid particlesof a mixture of an o-acylaminophenol color-former for the cyan imagecapable of forming a quinoneimine dye with a phenylenediamine developer,and a substantially water-insoluble, low molecular weight, organiccrystalloidal material having a boiling point above about 175 C., saidcrystalloidal material having a high solvent action for the color-formerand for the dye formed therefrom and being permeable to photographicprocessing solutions, the nature and proportions of the color-former andcrystalloidal material being so chosen that particles thereof are liquidunder conditions of coating and processing the emulsion, said redsensitive emulsion being sensitized to the red with at least onesensitizing dye selected from the group consisting of those dyesrepresented by the following general formula:

cyclic: aryh groups on the: benzeneseries Zr naps-ea sents; thenonemetallim atoms; necessary: to: come plate: a: heteroeyclie nucleus;of; the.- benzoislaiazale;v

series: and X represents; am anion=..

'72. A. red; sensitive: gelatino siluer-halide emul sion: foncQlor:photegraphy' cfintaining; dispersed: therein; finely divided. liquidparticles of a. mix? ture off an; o.-aey1am-inophenol colon-former; ionthe; cyan image capable ot fOFIIliHg; a q uinoner' imine. dye with aphenylenediamine; developer;, and a.- substantiallywater-insoluble; 10W:molecs ula-r weight, organic; crystalloidalmaterial have ing; a boilingpoint. aboyt about 1'75? said. crystalloidal material, having, a. high;solvent; ace tion for the color-former and for the dye formed therefromand being permeable to photographic processing solutions, the nature andproportions of the color-former and crystalloidal material being sochosen that particles thereofare liquid under conditions of coating. andprocessing the emulsion, said red sensitive 8111111510111 beingsensitized to the red with at least one sensitizing dye selected fromthe group consisting of those dyes represented by the following formula:

8. A yellow-green sensitive gelatino-silverhalide emulsion for colorphotography containing dispersed therein finely divided liquid particlesof a mixture of a 5-pyrazolone color-former for the magenta imagecapable of. forming an azomethine dye with. a phenylenediaminedeveloper, and a substantially water-insoluble, low molecular weight,organic, crystalloi'dal material having a boiling point above about 175"C., said crystalloidal material having a high. solvent action for thecolor-former and for the dye formed therefrom, and being permeable tophotographic pronessingvsolutions, the natuiseiandspmportions: of the"color-former, and crystalloidal. material being: so chosen thatparticles; i'zhereof are.- liquicl' under conditions of: coating and.DIQOW essing the emulsion, said yellow-green: sensitive: emulsion beingsensitized to: the yellow -green with at least one sensitizing dyeselected. from the group consisting of those dyes represented by thefollowing general formulas:

r x o e legu e-1237c one;

, heterocyclicxnuoleus Of the: quinoline series;

9:. A1; yellow-green; sensitive gelatino-silvers halide: emulsionioncolorphotography contain-,- in dispersed therein: finely divided:liquid particles; of: azmixture: of a, Fz-IJYrazolonaeolor-iorm-' erfor: the magenta image capable of forming; an. azomethine dye with; aphenylenediamine. de-v velopen, and a substantially Water-insoluble lowmolecular weight, organic, crystal-lodial materialhaving a. boilingpoint above about 1-75 said crystalloidala material having a highsolvent. 346: tion ior-theoolOr-former and for the dye-formed therefrom,andzbeing permeable to photo laphia processing.- solutions, the, natureand proportions, of: the color-former and crystalloidal. materialbeing;so chosen: that particles thereofare liquid under conditions of coatingand processing the emulsion, said yellow-green sensitive emulsion beingsensitized to, the yellow-green with at least one sensitizing d'yeselected from the group" consisting of those dyes represented by thefollowing general formula;

iI-R,

wherein D2 represents a divalent saturated all-- phatic radicalcontaining from 1' to 4' carbon atoms, Re -represents a primary alkylgroup: con;- taining from I tore carbon atoms, X1 represents an anionand: Z3 represents. the non-metallic, atoms, necessary to; complete, a.heterocyclic: nucleus of the quinoiine: series.

I02 A yellow-green sensitive gelatino-silverhalide emulsion for colorphotography contain-- ingv dispersed therein finely divided-1 liquidparticles ofi amixture of a. 5-pyrazolone color-former tor themagentaimage capable of forming an: azomethine dye with avphenylenediamine developer; and a substantially water-insoluble, lowmolecular weight, organic, crystalloidal material: having: aboilingspoint above. about 1:75" 0., said crystalloidal material having a, highsolvent action for te color-former and for the dye formed therefrom, andbeing! permeable to photographic processing solutions, the natur andproporti ns. of the color-former and crystalloidal material belng sochosen that particles thereof are liquid under conditions of coating andprocessing the emulsion, said yellow-green sensitive emulsion beingsensitized to the yellow-green with at least one sensitizing dyeselected from the group consisting of those dyes represented by thefollowing formula:

IH2 COOH 11. A sensitive silver halide emulsion for color photographyselected from the group consisting of (I) a red sensitive silver halideemulsion con taining dispersed therein finely divided liquid particlesof a mixture of a phenolic color-former for the cyan image capable offorming a quinoneimine dye with a phenylenediamine developer, and asubstantially water-insoluble, low molecular weight, organic,crystalloidal material having a boiling point above about 175 C., saidcrystalloidal material having a high solvent action for the color-formerand for the dye formed therefrom, and being permeable to photographicprocessing solutions, the nature and proportions of the color-former andcrystalloidal material being so chosen that particles thereof are liquidunder conditions of coating and processing the emulsion, said redsensitive emulsion being sensitized to the red with at least onesensitizing dye selected from the group consisting of those dyesrepresented by the following general formulas:

wherein D and D1 each represents a divalent aliphatic hydrocarbonradical containing from 1 to 4 carbon atoms, R and R4 represent a memberselected from the group consisting of a hydrogen atom and an alkyl groupconsisting from 1 to 4 carbon atoms, Z and Z1 each represents thenon-metallic atoms necessary to complete a heterocyclic nucleus selectedfrom the group consisting of heterocyclic nuclei of the benzothiazoleseries, heterocyclic nuclei of the benzoselenazole series, heterocyclicnuclei of the naphthothiazole series and heterocyclic nuclei of thenaphthoselenazole series, R1 and R3 each represents an alkyl groupcontaining from 1 to 2 carbon atoms, R2 represents a monocyclic arylgroup of the benzene series, and X represents an anion, and (II) ayellow-green sensitive silver halide emulsion containing dispersedtherein finely divided liquid particles of a mixture of a ketomethylenecolorformer for the magenta image capable of forming a quinoneimine dyewith a phenylenediamine developer, and a substantially water-insoluble,

iv-p 1-0 H low molecular weight, organic, crystalloidal material havinga boiling point above about C., said crystalloidal material having ahigh solvent action for the color-former and for the dye formedtherefrom, and being permeable to photographic processing solutions, thenature and proportions of the color-former and crystalloidal materialbeing so chosen that particles thereof are liquid under conditions ofcoating and processing the emulsion, said yellow-green sensitive silverhalide emulsion being sensitized to the yellow-green with at least onesensitizing dye selected from the group consisting of those dyesrepresented by the following general formulas:

wherein R4 and R5 each represents an alkyl group containing from 1 to 4carbon atoms, X1 represents an anion, D2 and D3 each represents adivalent aliphatic hydrocarbon radical containing from 1 to 4 carbonatoms, and Z3 represents the non-metallic atoms necessary to complete aheterocyclic nucleus of the quinoline series.

JOHN SPENCE.

BURT H. CARROLL.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,148,979 Dieterle Feb. 28, 1939 2,148,980 Dieterle Feb. 28,1939 2,213,238 Broolcer et al. Sept. 3, 1940 2,231,658 Brooker et al.Feb. 11, 1941 2,304,940 Mannes et al Dec. 15, 1942 2,322,027 Jelley etal June 15, 1943 2,478,366 Brooker et a1 Aug. 9, 1949 2,515,913 VanZandt et al. July 18, 1950

11. A SENSITIVE SILVER HALIDE EMULSION FOR COLOR PHOTOGRAPHY SELECTEDFROM THE GROUP CONSISTING OF (I) A RED SENSITIVE SILVER HALIDE EMULSIONCONTAINING DISPERSED THEREIN FINELY DIVIDED LIQUID PARTICLES OF AMIXTURE OF A PHENOLIC COLOR-FORMER FOR THE CYAN IMAGE CAPABLE OF FORMINGA QUINONEIMINE DYE WITH A PHENYLENEDIAMINE DEVELOPER, AND ASUBSTANTIALLY WATER-INSOLUBLE, LOW MOLECULAR WEIGHT, ORGANIC,CRYSTALLOIDAL MATERIAL HAVING A BOILING POINT HAVING ABOUT 175* C., SAIDCRYSTALLOIDAL MATERIAL HAVING A HIGH SOLVENT ACTION FOR THE COLOR-FORMERAND FOR THE DYE FORMED THEREFROM, AND BEING PERMEABLE TO PHOTOGRAPHICPROCESSING SOLUTIONS, THE NATURE AND PROPORTIONS OF THE COLOR-FORMER ANDCRYSTALLOIDAL MATERIAL BEING SO CHOSEN THAT PARTICLES THEREOF ARE LIQUIDUNDER CONDITIONS OF COATING AND PROCESSING THE EMULSION, SAID REDSENSITIVE EMULSION BEING SENSITIZED TO THE RED WITH AT LEAST ONESENSITIZING DYE SELECTED FROM THE GROUP CONSISTING OF THOSE DYESREPRESENTED BY THE FOLLOWING GENERAL FORMULAS: